JP2022151688A - Solar cell module - Google Patents

Abstract

To provide a solar cell module capable of keeping power generation efficiency even after long exposure to high-illuminance light.SOLUTION: In a solar cell module, a plurality of photoelectric conversion elements including a first electrode, an electron transport layer, a perovskite layer, a hole transport layer, and a second electrode are provided on a substrate. In the two adjacent photoelectric conversion elements, the first electrodes are electrically connected to each other, the electron transport layer, the perovskite layer, and the hole transport layer are separated by a gap, the second electrode in one photoelectric conversion element and the first electrode in the other photoelectric conversion element are electrically connected, and in the one photoelectric conversion element, the first electrode, the electron transport layer, and the perovskite layer are partitioned by the hole transport layer.SELECTED DRAWING: Figure 10

Description

The present invention relates to solar cell modules.

In recent years, solar cells using photoelectric conversion elements are expected to find wide-ranging applications not only from the standpoint of replacing fossil fuels and countering global warming, but also as independent power sources that do not require battery replacement or power supply wiring. In addition, solar cells as self-sustaining power sources are attracting a great deal of attention as one of the energy harvesting technologies required for IoT (Internet of Things) devices, artificial satellites, and the like.

Solar cells include organic solar cells such as dye-sensitized solar cells, organic thin-film solar cells, and perovskite solar cells, in addition to inorganic solar cells using silicon that have been widely used. Perovskite solar cells can be manufactured using conventional printing methods without using electrolytes containing iodine or organic solvents, and are therefore advantageous in terms of improved safety and reduced manufacturing costs.

In addition, with respect to organic thin-film solar cells and perovskite solar cells, it is known to electrically connect a plurality of spatially divided photoelectric conversion elements in a series circuit to increase the output voltage. (See Patent Document 1, for example).

An object of the present invention is to provide a solar cell module capable of maintaining power generation efficiency even after being exposed to high-intensity light for a long period of time.

A solar cell module of the present invention as a means for solving the above problems is a photoelectric conversion element having a first electrode, an electron transport layer, a perovskite layer, a hole transport layer, and a second electrode on a substrate. A plurality of solar cell modules,
In the two adjacent photoelectric conversion elements,
the first electrodes are electrically connected to each other;
the electron transport layer, the perovskite layer and the hole transport layer are separated by a gap;
the second electrode of one photoelectric conversion element and the first electrode of the other photoelectric conversion element are electrically connected,
In the one photoelectric conversion element, the first electrode, the electron transport layer and the perovskite layer are separated by the hole transport layer.

ADVANTAGE OF THE INVENTION According to this invention, the photoelectric conversion cell module which can maintain a power generation efficiency even after being exposed to high illumination intensity light for a long time can be provided.

FIG. 1 shows a schematic diagram showing an example of a cross-sectional structure of a device in the process of fabrication in Example 1. FIG. FIG. 2 is a schematic diagram showing an example of a cross-sectional structure of a device in the process of fabrication in Example 1. FIG. FIG. 3 shows a schematic diagram showing an example of a cross-sectional structure of a device in the process of fabrication in Example 1. FIG. FIG. 4 is a schematic diagram showing an example of a cross-sectional structure of a device in the process of fabrication in Example 1. FIG. FIG. 5 shows a schematic diagram showing an example of a top view of a device in the process of fabrication in Example 1. FIG. FIG. 6 is a schematic diagram showing an example of a cross-sectional structure of a device in the process of fabrication in Example 1. FIG. FIG. 7 shows a schematic diagram showing an example of a cross-sectional structure of a device in the process of fabrication in Example 1. FIG. FIG. 8 shows a schematic diagram showing an example of a top view of a device in the process of fabrication in Example 1. FIG. FIG. 9 shows a schematic diagram showing an example of a cross-sectional structure of a device in the process of fabrication in Example 1. FIG. FIG. 10 shows a schematic diagram showing an example of the cross-sectional structure of the devices fabricated in Examples 1 and 4. FIG.

(solar cell module)
The solar cell module of the present invention means a device capable of converting light energy into electric energy or electric energy into light energy, and is applied to solar cells, photodiodes and the like.
The solar cell module in the present invention is
In the two adjacent photoelectric conversion elements,
the first electrodes are electrically connected to each other;
the electron transport layer, the perovskite layer and the hole transport layer are separated by a gap;
the second electrode of one photoelectric conversion element and the first electrode of the other photoelectric conversion element are electrically connected,
In the one photoelectric conversion element, the first electrode, the electron transport layer and the perovskite layer are separated by the hole transport layer.

The solar cell module of the present invention preferably has a plurality of photoelectric conversion elements on a substrate, further includes a second substrate different from the substrate described above, a sealing member, and optionally other members. .

This is based on the knowledge that the power generation efficiency of conventional solar cell modules may be significantly reduced after being exposed to high-intensity light for a long period of time. Specifically, conventional solar cell modules have extended porous titanium oxide layers and perovskite layers, and electron recombination due to diffusion occurs frequently. , there is a problem that the power generation efficiency may be greatly reduced.

On the other hand, in the solar cell module of the present invention, in at least two photoelectric conversion elements separated by a gap, the first electrode, the electron transport layer, and the perovskite layer are separated by the hole transport layer. As a result, the solar cell module of the present invention has a cut perovskite layer, which reduces the recombination of electrons due to diffusion. Therefore, the solar cell module maintains power generation efficiency even after being exposed to high-intensity light for a long period of time. It is possible to
Another problem is that the adhesion between the hole transport layer and the second electrode is low, so that they are easily peeled off.

<Substrate>
The shape, structure, and size of the substrate are not particularly limited, and can be appropriately selected according to the purpose. In addition, below, the above-mentioned board|substrate may be called a 1st board|substrate.
The material of the first substrate is not particularly limited as long as it has translucency and insulating properties, and can be appropriately selected depending on the purpose. Examples thereof include glass, plastic film, and ceramics. Among these, materials having heat resistance to the firing temperature are preferable when the step of firing is included when forming the electron transport layer as described later. Moreover, as the first substrate, one having flexibility is preferable.

<First electrode>
The structure of the first electrode is not particularly limited and can be appropriately selected according to the purpose.
The first electrodes are separated by the hole transport layer in the photoelectric conversion element. This can prevent electron diffusion.
Here, the expression that the first electrode is separated by the hole transport layer means that the first electrode is divided into at least two by the hole transport layer, one first electrode and the other. is discontinuous with said first electrode of and has said hole transport layer therebetween.

The material of the first electrode is not particularly limited as long as it has conductivity, and can be appropriately selected according to the purpose. Examples thereof include transparent conductive metal oxides, carbon, and metals.

Examples of transparent conductive metal oxides include indium tin oxide (hereinafter referred to as "ITO"), fluorine-doped tin oxide (hereinafter referred to as "FTO"), and antimony-doped tin oxide (hereinafter referred to as "ATO"). ), niobium-doped tin oxide (hereinafter referred to as “NTO”), aluminum-doped zinc oxide, indium-zinc oxide, niobium-titanium oxide, and the like.
Examples of carbon include carbon black, carbon nanotubes, graphene, and fullerene.
Examples of metals include gold, silver, aluminum, nickel, indium, tantalum, and titanium.
These may be used individually by 1 type, and may use 2 or more types together. Among these, transparent conductive metal oxides with high transparency are preferred, and ITO, FTO, ATO, and NTO are more preferred.

The average thickness of the first electrode is not particularly limited, and can be appropriately selected according to the purpose. Note that when the material of the first electrode is carbon or metal, the average thickness of the first electrode is preferably an average thickness that can provide translucency.

The first electrode can be formed by known methods such as sputtering, vapor deposition, and spraying.

Moreover, the first electrode is preferably formed on the substrate, and an integrated commercial product in which the first electrode is formed on the substrate in advance can be used.
Commercially integrated products include, for example, FTO-coated glass, ITO-coated glass, zinc oxide:aluminum-coated glass, FTO-coated transparent plastic film, and ITO-coated transparent plastic film. Other integrated commercial products include, for example, transparent electrodes obtained by doping tin oxide or indium oxide with cations or anions having different valences, or metals with a structure that allows light to pass through, such as mesh or stripes. Examples include a glass substrate provided with electrodes.
These may be used singly, or two or more of them may be mixed or laminated together. Also, a metal lead wire or the like may be used together for the purpose of lowering the electrical resistance value. Alternatively, the electrodes in the integrated commercial product may be appropriately processed to produce a substrate on which a plurality of first electrodes are formed in order to produce a solar cell module to be described later.

Examples of materials for the metal lead wire include aluminum, copper, silver, gold, platinum, and nickel.
Metal lead wires can be used together by, for example, forming them on a substrate by vapor deposition, sputtering, pressure bonding, etc., and providing a layer of ITO or FTO thereon, or providing them on top of ITO or FTO.

<Electron transport layer>
The electron transport layer means a layer that transports electrons generated in the perovskite layer, which will be described later, to the first electrode. For this reason, the electron transport layer is preferably arranged adjacent to the first electrode.
The electron transport layers are separated by the hole transport layers in the photoelectric conversion device. Thereby, electron diffusion can be prevented.

The shape and size of the electron transport layer are not particularly limited, and can be appropriately selected according to the purpose.

The structure of the electron-transporting layer is not particularly limited and can be appropriately selected depending on the intended purpose. Among these, a multilayer is preferable, and it is more preferable to consist of a layer having a dense structure (hereinafter sometimes referred to as a dense layer) and a layer having a porous structure (hereinafter sometimes referred to as a porous layer). preferable. Moreover, it is preferable that the dense layer is arranged closer to the first electrode than the porous layer.

The dense layer contains an electron transport material.
The electron-transporting material is not particularly limited and can be appropriately selected depending on the intended purpose, but a semiconductor material is preferred.

The semiconductor material is not particularly limited, and known materials can be used. Examples thereof include single semiconductors and compounds having compound semiconductors.
Examples of single semiconductors include silicon and germanium.
Examples of compound semiconductors include metal chalcogenides.
Examples of metal chalcogenides include metal oxides (oxide semiconductors), metal sulfides, metal selenides, and metal tellurides.
Examples of metal oxides (oxide semiconductors) include oxides of titanium, tin, zinc, iron, tungsten, zirconium, hafnium, strontium, indium, cerium, yttrium, lanthanum, vanadium, niobium, and tantalum.
Examples of metal sulfides include sulfides of cadmium, zinc, lead, silver, antimony, bismuth, and the like.
Metal selenides include, for example, selenides of cadmium, lead, and the like.
Metal tellurides include, for example, tellurides such as cadmium.
Other compound semiconductors include phosphides such as zinc, gallium, indium and cadmium, gallium arsenide, copper-indium-selenide and copper-indium-sulfide.
Among these, metal oxides (oxide semiconductors) are preferable, and it is more preferable to contain at least one of titanium oxide, zinc oxide, tin oxide, and niobium oxide, and it is particularly preferable to contain tin oxide.
These may be used individually by 1 type, and may use 2 or more types together. The crystal type of the semiconductor material is not particularly limited and can be appropriately selected depending on the purpose, and may be single crystal, polycrystal, or amorphous.

The dense layer contains at least one of a phosphonic acid compound, a boronic acid compound, a sulfonic acid compound, a silyl halide compound, and an alkoxysilyl compound on the electron transport material on the surface of the perovskite layer. is preferred. By containing these compounds on the electron-transporting material on the surface of the perovskite layer side of the dense layer, the physical properties of the interface can be expected to be controlled. In other words, by coating the electron-transporting material with these compounds on the surface of the dense layer on the perovskite layer side, it is expected that interfacial resistance will be reduced and electron transfer will be smooth.
These compounds may be combined with the electron transport material. Bonds include, for example, covalent bonds, ionic bonds, and the like.

The compound is at least one of a phosphonic acid compound, a boronic acid compound, a sulfonic acid compound, a silyl halide compound, and an alkoxysilyl compound.
From the viewpoint of compatibility with the perovskite layer, the compound preferably has a nitrogen atom.

The phosphonic compound is not particularly limited as long as it is a compound containing a phosphonic acid group, and can be appropriately selected depending on the intended purpose. A specific example will be described later.

The boronic acid compound is not particularly limited as long as it is a compound containing a boronic acid group, and can be appropriately selected depending on the purpose. A specific example will be described later.

The sulfonic acid compound is not particularly limited as long as it is a compound containing a sulfonic acid group, and can be appropriately selected depending on the purpose. A specific example will be described later.

The silyl halide compound is not particularly limited as long as it is a compound containing a silyl halide group, and can be appropriately selected depending on the intended purpose. A specific example will be described later.

The alkoxysilyl compound is not particularly limited as long as it is a compound containing an alkoxysilyl group, and can be appropriately selected depending on the purpose. A specific example will be described later.

The molecular weight of the compound is not particularly limited and can be appropriately selected depending on the intended purpose.

The compound is represented, for example, by the following general formula (4).

Ｒ３は、２価のアリール基、又は２価のヘテロ環を表し、Ｒ４は、ホスホン酸基、ボロン酸基、スルホン酸基、ハロゲン化シリル基、又はアルコキシシリル基を表す。Ｒ１又はＲ２と、Ｒ３と、Ｎとは、一緒になって環構造を形成していてもよい。

R3 represents a divalent aryl group or a divalent heterocycle, and R4 represents a phosphonic acid group, boronic acid group, sulfonic acid group, halogenated silyl group or alkoxysilyl group. R1 or R2, R3 and N may together form a ring structure.

Examples of the compound include the following compounds.

The thickness of the dense layer is not particularly limited and can be appropriately selected depending on the intended purpose.

The surface of the dense layer on the perovskite layer side is preferably as smooth as possible. As an index of smoothness, the smaller the roughness factor, the better. However, considering the relationship with the average thickness of the dense layer, the roughness factor of the perovskite layer side of the dense layer is preferably 20 or less, more preferably 10 or less. The lower limit of the roughness factor is not particularly limited and can be appropriately selected depending on the purpose.
The roughness factor is the ratio of the actual surface area to the apparent surface area, and is also called Wenzel's roughness factor. The actual surface area can be measured, for example, by measuring the BET specific surface area, and the roughness factor can be obtained by dividing the value by the apparent surface area.

The method for producing the dense layer is not particularly limited and can be appropriately selected depending on the intended purpose. etc.
Vacuum film forming methods include, for example, a sputtering method, a pulse laser deposition method (PLD method), an ion beam sputtering method, an ion assist method, an ion plating method, a vacuum vapor deposition method, an atomic layer deposition method (ALD method), Chemical vapor deposition method (CVD method) etc. are mentioned.
The wet film-forming method includes, for example, a sol-gel method. The sol-gel method is a method in which a gel is produced from a solution through chemical reactions such as hydrolysis and polymerization/condensation, and then heat treatment is performed to promote densification. When the sol-gel method is used, the method of applying the sol solution is not particularly limited and can be appropriately selected depending on the purpose. method, blade coating method, gravure coating method, and wet printing methods include letterpress, offset, gravure, intaglio, rubber plate, screen printing and the like. The temperature for the heat treatment after applying the sol solution is preferably 80° C. or higher, more preferably 100° C. or higher.

The method of applying the compound onto the electron transport material is not particularly limited and can be appropriately selected according to the purpose. A method of drying can be mentioned.
The coating method is not particularly limited and can be appropriately selected depending on the intended purpose. mentioned.
The temperature for the drying treatment after applying the solution is preferably 40° C. or higher, more preferably 50° C. or higher.

<<Porous layer>>
The porous layer is not particularly limited as long as it contains an electron-transporting material and is less dense than the dense layer (that is, a layer that is porous), and can be appropriately selected according to the purpose. By forming the electron transport layer on the porous surface, it is possible to stabilize the crystal growth of the perovskite layer.
It should be noted that "not denser than the dense layer" means that the packing density of the porous layer is lower than the packing density of the dense layer.

Examples of materials for the electron transport layer in the porous layer include semiconductor materials in the dense layer. Among these, titanium oxide is preferred.

The film thickness of the porous layer is not particularly limited and can be appropriately selected depending on the intended purpose.

<Perovskite layer>
The perovskite layer means a layer that contains a perovskite compound represented by the following general formula (1) and absorbs light to sensitize the electron transport layer. Therefore, the perovskite layer is preferably arranged adjacent to the electron transport layer.
XαYβZγ General formula (1)
In general formula (1), the ratio of α:β:γ is 3:1:1, and β and γ represent integers greater than 1. X represents a halogen atom, Y represents an amino group-containing organic compound, and Z represents a metal ion.

The perovskite layers are separated by the hole transport layer and further separated by the second electrode in the photoelectric conversion element. Thereby, electron diffusion can be prevented.

The shape and size of the perovskite layer are not particularly limited, and can be appropriately selected according to the purpose.

A perovskite compound is a composite material of an organic compound and an inorganic compound, and is represented by the following general formula (1).
XαYβMγ General formula (1)
In the general formula (1) above, the ratio of α:β:γ is 3:1:1, and β and γ represent integers greater than 1. Further, for example, X can be a halogen ion, Y can be an ion of an organic compound having an amino group, and M can be a metal ion.

X in the above general formula (1) is not particularly limited and can be appropriately selected depending on the intended purpose. Examples thereof include halogen ions such as chlorine, bromine and iodine. These may be used individually by 1 type, and may use 2 or more types together.

Examples of Y in the general formula (1) include alkylamine compound ions such as methylamine, ethylamine, n-butylamine and formamidine, cesium, potassium and rubidium. In the case of the lead halide-methylammonium perovskite compound, when the halogen ion is Cl, the peak λmax of the light absorption spectrum is about 350 nm, when it is Br, it is about 410 nm, and when it is I, it is about 540 nm. Due to the shift to the side, the available spectral width (bandwidth) is different.

M in the general formula (1) is not particularly limited and can be appropriately selected depending on the intended purpose. Examples thereof include metal ions such as lead, indium, antimony, tin, copper and bismuth.

Moreover, the perovskite layer preferably exhibits a layered perovskite structure in which a layer composed of a metal halide and a layer in which organic cation molecules are arranged are alternately laminated.

The method for forming the perovskite layer is not particularly limited and can be appropriately selected depending on the intended purpose. etc.
As a method for forming a perovskite layer, for example, a solution in which a metal halide is dissolved or dispersed is applied, dried, and then immersed in a solution in which an alkylamine halide is dissolved to form a perovskite compound. A stepwise precipitation method and the like can be mentioned.
Furthermore, as a method for forming a perovskite layer, for example, while applying a solution in which a metal halide and an alkylamine halide are dissolved or dispersed, a poor solvent (a solvent with low solubility) for the perovskite compound is added to precipitate crystals. and the like. Methods for forming the perovskite layer include, for example, a method of vapor-depositing a metal halide in a gas filled with methylamine or the like.
Among these, a method of precipitating crystals by adding a poor solvent for the perovskite compound while applying a solution in which a metal halide and an alkylamine halide are dissolved or dispersed is preferred.

The method of applying the solution is not particularly limited and can be appropriately selected depending on the intended purpose. Moreover, as a method of applying the solution, for example, a method of precipitating in a supercritical fluid using carbon dioxide or the like may be used.

Also, the perovskite layer may contain a sensitizing dye.
The method of forming the perovskite layer containing the sensitizing dye is not particularly limited and can be appropriately selected according to the purpose. and a method of adsorbing a sensitizing dye.

The sensitizing dye is not particularly limited as long as it is a compound that is photoexcited by the excitation light used, and can be appropriately selected depending on the intended purpose.
Examples of sensitizing dyes include metal complex compounds, coumarin compounds, polyene compounds, indoline compounds, thiophene compounds, cyanine dyes, merocyanine dyes, 9-arylxanthene compounds, triarylmethane compounds, phthalocyanine compounds, and porphyrin compounds. .
As metal complex compounds, for example, JP-A-7-500630, JP-A-10-233238, JP-A-2000-26487, JP-A-2000-323191, JP-A-2001-59062, etc. Examples thereof include metal complex compounds described above.
Examples of coumarin compounds include, for example, JP-A-10-93118, JP-A-2002-164089, JP-A-2004-95450, J. Am. Phys. Chem. C, 7224, Vol. 111 (2007) and the like.
As the polyene compound, for example, JP-A-2004-95450, Chem. Commun. , 4887 (2007) and the like.
Examples of indoline compounds include, for example, JP-A-2003-264010, JP-A-2004-63274, JP-A-2004-115636, JP-A-2004-200068, JP-A-2004-235052, J. Am. Am. Chem. Soc. , 12218, Vol. 126 (2004), Chem. Commun. , 3036 (2003), Angew. Chem. Int. Ed. , 1923, Vol. 47 (2008), and the like.
As the thiophene compound, for example, J. Am. Am. Chem. Soc. , 16701, Vol. 128 (2006); Am. Chem. Soc. , 14256, Vol. 128 (2006) and the like.
As the cyanine dye, for example, JP-A-11-86916, JP-A-11-214730, JP-A-2000-106224, JP-A-2001-76773, JP-A-2003-7359, etc. cyanine dyes and the like.
As the merocyanine dye, for example, JP-A-11-214731, JP-A-11-238905, JP-A-2001-52766, JP-A-2001-76775, JP-A-2003-7360, etc. and merocyanine dyes.
Examples of 9-arylxanthene compounds include 9-arylxanthene compounds described in JP-A-10-92477, JP-A-11-273754, JP-A-11-273755, JP-A-2003-31273, etc. etc.
Examples of triarylmethane compounds include triarylmethane compounds described in JP-A-10-93118, JP-A-2003-31273, and the like.
Examples of phthalocyanine compounds and porphyrin compounds include those described in JP-A-9-199744, JP-A-10-233238, JP-A-11-204821, JP-A-11-265738, J. Am. Phys. Chem. , 2342, Vol. 91 (1987), J. Phys. Chem. B, 6272, Vol. 97 (1993), Electroanal. Chem. , 31, Vol. 537 (2002), JP-A-2006-032260, J.P. Porphyrins Phthalocyanines, 230, Vol. 3 (1999), Angew. Chem. Int. Ed. , 373, Vol. 46 (2007), Langmuir, 5436, Vol. 24 (2008), phthalocyanine compounds, porphyrin compounds, and the like.
Among these, metal complex compounds, indoline compounds, thiophene compounds, and porphyrin compounds are preferred.

<Organic salt, inorganic salt>
The photoelectric conversion device preferably contains at least one of an organic salt and an inorganic salt between the perovskite layer and the hole transport layer.
By containing the salt between the perovskite layer and the hole transport layer, the photoelectric conversion device can be expected to control the physical properties of the interface.
When the perovskite layer is a perovskite layer, the salt is preferably different from the salt forming the perovskite layer.

The salt is not particularly limited and can be appropriately selected depending on the purpose. Especially when a perovskite compound is used for the perovskite layer, it is preferable that the cation has a halogen atom in terms of compatibility. . Halogen includes, for example, chlorine, iodine, bromine, and the like.

The organic salt is preferably an amine hydrohalide from the viewpoint of compatibility, particularly when a perovskite compound is used in the perovskite layer.
The inorganic salt is preferably an alkali metal halide from the viewpoint of compatibility, particularly when a perovskite compound is used in the perovskite layer. Alkali metals include, for example, lithium, sodium, potassium, rubidium, and cesium.

Examples of the amine hydrohalide include n-butylamine hydrobromide, n-butylamine hydroiodide, n-hexylamine hydrobromide, and n-hexylamine hydroiodide. , n-decylamine hydrobromide, n-octadecylamine hydroiodide, pyridine hydrobromide, aniline hydroiodide, hydrazine dihydrobromide, ethylenediamine dihydroiodide, 2- phenylethylamine hydroiodide, phenylenediamine dihydrochloride, diphenylamine hydrobromide, diphenylamine hydroiodide, benzylamine hydroiodide, 4-diphenylaminophenethylamine hydroiodide, etc. mentioned.
Examples of the alkali metal halides include cesium iodide, cesium bromide, rubidium iodide, and potassium iodide.

The method for disposing at least one of an organic salt and an inorganic salt between the perovskite layer and the hole transport layer is not particularly limited and can be appropriately selected depending on the purpose. Second, a method of applying a solution containing the salt, drying it, and then forming a hole transport layer thereon can be mentioned. Examples of the solution include an aqueous solution and an alcohol solution.
The coating method is not particularly limited and can be appropriately selected depending on the intended purpose. mentioned.
The temperature for the drying treatment after applying the solution is not particularly limited, and can be appropriately selected according to the purpose.

<Hole transport layer>
A hole transport layer means a layer that transports holes generated in the perovskite layer to a second electrode described later. Therefore, the hole transport layer is preferably arranged adjacent to the perovskite layer with the salt interposed therebetween.
The hole transport layer is formed so as to separate the first electrode, the electron transport layer and the perovskite layer in the photoelectric conversion element. Thereby, electron diffusion can be prevented.
The hole transport layer is separated by the second electrode in the photoelectric conversion element.

The hole transport layer is not particularly limited as long as it can separate the electron transport layer and the perovskite layer in at least two photoelectric conversion elements adjacent to each other, and can be appropriately selected depending on the purpose.
By separating the first electrode, the electron transport layer, and the perovskite layer in at least two mutually adjacent photoelectric conversion elements by the hole transport layer, the recombination of electrons due to diffusion is reduced. It is possible to maintain power generation efficiency even after being exposed to high-intensity light for a long period of time.

The hole-transporting layer contains a solid hole-transporting material and optionally other materials.
The solid hole-transporting material (hereinafter sometimes simply referred to as "hole-transporting material") is not particularly limited as long as it has the property of transporting holes, and can be appropriately selected according to the purpose. However, it is preferable to contain an organic compound.

When an organic compound is used as the hole-transporting material, conventionally known materials can be used, and examples of the hole-transporting material include low-molecular-weight compounds, high-molecular-weight compounds, and mixtures thereof.
When a polymer compound is used as the hole-transporting material, it preferably contains a polymer having a molecular weight of 2000 or more.

The polymer material used for the hole transport layer is not particularly limited and can be appropriately selected depending on the intended purpose. compound and the like.
Examples of polythiophene compounds include poly(3-n-hexylthiophene), poly(3-n-octyloxythiophene), poly(9,9'-dioctyl-fluorene-co-bithiophene), poly(3,3'''-didodecyl-quaterthiophene), poly(3,6-dioctylthieno[3,2-b]thiophene), poly(2,5-bis(3-decylthiophen-2-yl)thieno[3,2- b]thiophene), poly(3,4-didecylthiophene-co-thieno[3,2-b]thiophene), poly(3,6-dioctylthieno[3,2-b]thiophene-co-thieno[3 ,2-b]thiophene), poly(3,6-dioctylthieno[3,2-b]thiophene-co-thiophene), poly(3,6-dioctylthieno[3,2-b]thiophene-co-bithiophene) ) and the like.
Examples of polyphenylene vinylene compounds include poly[2-methoxy-5-(2-ethylhexyloxy)-1,4-phenylene vinylene], poly[2-methoxy-5-(3,7-dimethyloctyloxy)-1 ,4-phenylenevinylene], poly[(2-methoxy-5-(2-ethylphexyloxy)-1,4-phenylenevinylene)-co-(4,4′-biphenylene-vinylene)], and the like. .
Examples of polyfluorene compounds include poly(9,9′-didodecylfluorenyl-2,7-diyl), poly[(9,9-dioctyl-2,7-divinylenefluorene)-alt-co- (9,10-anthracene)], poly[(9,9-dioctyl-2,7-divinylenefluorene)-alt-co-(4,4′-biphenylene)], poly[(9,9-dioctyl- 2,7-divinylenefluorene)-alt-co-(2-methoxy-5-(2-ethylhexyloxy)-1,4-phenylene)], poly[(9,9-dioctyl-2,7-diyl) -co-(1,4-(2,5-dihexyloxy)benzene)] and the like.
Examples of polyphenylene compounds include poly[2,5-dioctyloxy-1,4-phenylene] and poly[2,5-di(2-ethylhexyloxy-1,4-phenylene].
Examples of polyarylamine compounds include poly[(9,9-dioctylfluorenyl-2,7-diyl)-alt-co-(N,N'-diphenyl)-N,N'-di(p- hexylphenyl)-1,4-diaminobenzene], poly[(9,9-dioctylfluorenyl-2,7-diyl)-alt-co-(N,N'-bis(4-octyloxyphenyl)benzidine -N,N'-(1,4-diphenylene)], poly[(N,N'-bis(4-octyloxyphenyl)benzidine-N,N'-(1,4-diphenylene)], poly[( N,N'-bis(4-(2-ethylhexyloxy)phenyl)benzidine-N,N'-(1,4-diphenylene)], poly[phenylimino-1,4-phenylenevinylene-2,5-dioctyl oxy-1,4-phenylenevinylene-1,4-phenylene], poly[p-tolylimino-1,4-phenylenevinylene-2,5-di(2-ethylhexyloxy)-1,4-phenylenevinylene-1, 4-phenylene], poly[4-(2-ethylhexyloxy)phenylimino-1,4-biphenylene] and the like.
Examples of polythiadiazole compounds include poly[(9,9-dioctylfluorenyl-2,7-diyl)-alt-co-(1,4-benzo(2,1′,3)thiadiazole], poly( 3,4-didecylthiophene-co-(1,4-benzo(2,1′,3)thiadiazole) etc. Among them, considering carrier mobility and ionization potential, polythiophene compounds, polyaryl An amine compound is preferable, and at least one of compounds represented by the following general formula (2) and the following general formula (3) is more preferable.

上記一般式（２）におけるＡｒ１はアリール基を表す。アリール基としては、例えば、フェニル基、１－ナフチル基、９－アントラセニル基等が挙げられる。アリール基は、置換基を有していても良い。置換基としては、例えば、アルキル基、アルコキシ基、アリール基などが挙げられる。Ａｒ２、Ａｒ３及びＡｒ４はそれぞれ独立してアリーレン基、２価のヘテロ環基などを表す。アリーレン基としては、例えば、１，４－フェニレン、１，１’－ビフェニレン、９，９’－ジ－ｎ－ヘキシルフルオレン等が挙げられる。２価のヘテロ環基としては、例えば、２，５－チオフェン等が挙げられる。Ｒ１～Ｒ４は、それぞれ独立して、水素原子、アルキル基、アリール基などが挙げられる。アルキル基としては、例えば、メチル基、エチル基等が挙げられる。アリール基としては、例えば、フェニル基、２－ナフチル基等が挙げられる。前記アルキル基、及び前記アリール基は置換基を有していてもよい。

Ar1 in the general formula (2) represents an aryl group. Aryl groups include, for example, a phenyl group, a 1-naphthyl group, a 9-anthracenyl group and the like. The aryl group may have a substituent. Examples of substituents include alkyl groups, alkoxy groups, and aryl groups. Ar2, Ar3 and Ar4 each independently represent an arylene group, a divalent heterocyclic group, or the like. Arylene groups include, for example, 1,4-phenylene, 1,1'-biphenylene, 9,9'-di-n-hexylfluorene and the like. Examples of divalent heterocyclic groups include 2,5-thiophene and the like. R1 to R4 each independently include a hydrogen atom, an alkyl group, an aryl group, and the like. Examples of alkyl groups include a methyl group and an ethyl group. Aryl groups include, for example, a phenyl group and a 2-naphthyl group. The alkyl group and the aryl group may have a substituent.

Specific examples of the polymer represented by the general formula (2) include the following (A-01) to (A-22), but are not limited thereto.

前記一般式（３）中、Ｒ１～Ｒ５は、水素原子、ハロゲン原子、アルキル基、アルコキシ基、又はアリール基を表し、同一であっても異なっていてもよい。Ｘはカチオンを表す。Ｒ１及びＲ２、又はＲ２及びＲ３は、一緒になって環構造を形成していてもよい。

In general formula (3), R1 to R5 represent a hydrogen atom, a halogen atom, an alkyl group, an alkoxy group, or an aryl group, and may be the same or different. X represents a cation. R1 and R2 or R2 and R3 may together form a ring structure.

Examples of the halogen atom include chlorine atom, bromine atom, and iodine atom.
Examples of the alkyl group include alkyl groups having 1 to 6 carbon atoms. The alkyl group may be substituted with a halogen atom.
Examples of the alkoxy group include alkoxy groups having 1 to 6 carbon atoms.
Examples of the aryl group include a phenyl group.

The cation is not particularly limited and can be appropriately selected depending on the intended purpose. Examples thereof include alkali metal cations, phosphonium cations, iodonium cations, nitrogen-containing cations and sulfonium cations. Here, the nitrogen-containing cation means an ion having a positive charge on a nitrogen atom, and examples thereof include ammonium cation, pyridinium cation and imidazolium cation.

Specific examples of the compound represented by the general formula (3) include the following (B-1) to (B-28), but are not limited thereto.

Mass ratio of the polymer compound (2) having a repeating structure represented by the general formula (2) and the compound (3) represented by the general formula (3) in the hole transport layer [(2) :(3)] is not particularly limited and can be appropriately selected according to the purpose. ~1,000:300 is more preferred.

The hole-transporting layer may, for example, further contain other solid hole-transporting materials, and optionally other materials.
Other solid hole-transporting materials (hereinafter sometimes simply referred to as "hole-transporting materials") are not particularly limited as long as they have the property of transporting holes, and are appropriately selected according to the purpose. However, it preferably contains an organic compound.

When an organic compound is used as the hole-transporting material, the hole-transporting layer contains, for example, multiple types of compounds.

Examples of organic compounds include polymeric materials.
The polymer material used for the hole transport layer is not particularly limited and can be appropriately selected depending on the intended purpose. compound and the like.
Examples of polythiophene compounds include poly(3-n-hexylthiophene), poly(3-n-octyloxythiophene), poly(9,9'-dioctyl-fluorene-co-bithiophene), poly(3,3'''-didodecyl-quaterthiophene), poly(3,6-dioctylthieno[3,2-b]thiophene), poly(2,5-bis(3-decylthiophen-2-yl)thieno[3,2- b]thiophene), poly(3,4-didecylthiophene-co-thieno[3,2-b]thiophene), poly(3,6-dioctylthieno[3,2-b]thiophene-co-thieno[3 ,2-b]thiophene), poly(3,6-dioctylthieno[3,2-b]thiophene-co-thiophene), poly(3,6-dioctylthieno[3,2-b]thiophene-co-bithiophene) ) and the like.
Examples of polyphenylene vinylene compounds include poly[2-methoxy-5-(2-ethylhexyloxy)-1,4-phenylene vinylene], poly[2-methoxy-5-(3,7-dimethyloctyloxy)-1 ,4-phenylenevinylene], poly[(2-methoxy-5-(2-ethylphexyloxy)-1,4-phenylenevinylene)-co-(4,4′-biphenylene-vinylene)], and the like. .
Examples of polyfluorene compounds include poly(9,9′-didodecylfluorenyl-2,7-diyl), poly[(9,9-dioctyl-2,7-divinylenefluorene)-alt-co- (9,10-anthracene)], poly[(9,9-dioctyl-2,7-divinylenefluorene)-alt-co-(4,4′-biphenylene)], poly[(9,9-dioctyl- 2,7-divinylenefluorene)-alt-co-(2-methoxy-5-(2-ethylhexyloxy)-1,4-phenylene)], poly[(9,9-dioctyl-2,7-diyl) -co-(1,4-(2,5-dihexyloxy)benzene)] and the like.
Examples of polyphenylene compounds include poly[2,5-dioctyloxy-1,4-phenylene] and poly[2,5-di(2-ethylhexyloxy-1,4-phenylene].
Examples of polythiadiazole compounds include poly[(9,9-dioctylfluorenyl-2,7-diyl)-alt-co-(1,4-benzo(2,1′,3)thiadiazole], poly( 3,4-didecylthiophene-co-(1,4-benzo(2,1′,3)thiadiazole) and the like.

ただし、前記一般式（５）中、Ｒ３は、水素原子又はアルキル基を表す。 The hole-transporting layer may contain not only the above polymer compound but also a low-molecular-weight compound alone or a mixture of a low-molecular-weight compound and a high-molecular-weight compound.
The chemical structure of the low-molecular-weight hole-transporting material is not particularly limited. is mentioned. Examples of the oxadiazole compound include oxadiazole compounds disclosed in JP-B-34-5466, JP-A-56-123544, and the like.
Examples of triphenylmethane compounds include triphenylmethane compounds disclosed in JP-B-45-555.
Examples of pyrazoline compounds include pyrazoline compounds disclosed in JP-B-52-4188.
Examples of hydrazone compounds include hydrazone compounds disclosed in Japanese Patent Publication No. 55-42380.
Tetraarylbenzidine compounds include, for example, tetraarylbenzidine compounds disclosed in JP-A-54-58445.
The stilbene compounds include, for example, stilbene compounds disclosed in JP-A-58-65440 and JP-A-60-98437.
Examples of spirobifluorene compounds include, for example, JP-A-2007-115665, JP-A-2014-72327, JP-A-2001-257012, WO2004/063283, WO2011/030450, WO2011/45321, Examples thereof include spirobifluorene compounds disclosed in WO2013/042699 and WO2013/121835. Examples of thiophene oligomers include thiophene oligomers disclosed in JP-A-2-250881 and JP-A-2013-033868.
Among these low-molecular-weight hole-transporting materials, spirobifluorene compounds are preferred, and spirobifluorene compounds represented by the following general formula (5) are more preferred.

However, in said general formula (5), R3 represents a hydrogen atom or an alkyl group.

When a high-molecular compound and a low-molecular compound are mixed, the difference between their ionization potentials is preferably 0.2 eV or less. The ionization potential is the energy required to remove one electron from a molecule and is expressed in units of electron volts (eV). Although the method for measuring the ionization potential is not particularly limited, measurement by photoelectron spectroscopy is preferred.

Other materials contained in the hole transport layer are not particularly limited and can be appropriately selected depending on the intended purpose. Examples thereof include additives and oxidizing agents.

The additive is not particularly limited and can be appropriately selected depending on the intended purpose. metal iodides such as iron iodide and silver iodide; quaternary ammonium salts such as tetraalkylammonium iodide and pyridinium iodide; Bromine salts of quaternary ammonium compounds such as metal bromides, tetraalkylammonium bromide and pyridinium bromide, metal chlorides such as copper chloride and silver chloride, metal acetate salts such as copper acetate, silver acetate and palladium acetate, copper sulfate, Metal sulfates such as zinc sulfate, metal complexes such as ferrocyanate-ferricinium ion, ferrocene-ferricinium ion, sulfur compounds such as sodium polysulfide, alkylthiol-alkyldisulfide, viologen dyes, hydroquinone, etc., iodide 1,2-dimethyl-3-n-propylimidazolinium salt, 1-methyl-3-n-hexylimidazolinium iodide salt, 1,2-dimethyl-3-ethylimidazolium trifluoromethanesulfonate, Inorg. Chem. 35 (1996) 1168, basic compounds such as pyridine, 4-t-butylpyridine and benzimidazole, and lithium compounds such as lithium trifluoromethanesulfonylimide and lithium diisopropylimide.

The oxidizing agent is not particularly limited and can be appropriately selected depending on the intended purpose. , cobalt complexes, and the like. It should be noted that it is not necessary to oxidize the entire hole-transporting material with the oxidizing agent, and it is effective if it is partially oxidized. Moreover, the oxidizing agent may or may not be taken out of the system after the reaction.
By including an oxidizing agent in the hole-transporting layer, part or all of the hole-transporting material can be converted into radical cations, which improves the conductivity and increases the durability and stability of the output characteristics. Become.

The average thickness of the hole transport layer is not particularly limited and can be appropriately selected depending on the intended purpose. , more preferably 0.2 μm or more and 2 μm or less.

A hole transport layer can be formed directly on the perovskite layer. The method for producing the hole transport layer is not particularly limited and can be appropriately selected depending on the intended purpose. Among these, the wet film-forming method is particularly preferable, and the method of coating on the perovskite layer is more preferable in terms of manufacturing cost.
The wet film-forming method is not particularly limited and can be appropriately selected depending on the intended purpose. etc. Moreover, as the wet printing method, for example, letterpress, offset, gravure, intaglio, rubber plate, screen printing, and the like may be used.

Alternatively, the hole transport layer may be produced, for example, by film formation in a supercritical fluid or a subcritical fluid at a temperature and pressure lower than the critical point.
A supercritical fluid exists as a non-aggregating high-density fluid in a temperature and pressure range that exceeds the limit (critical point) where gas and liquid can coexist, does not aggregate even when compressed, has a critical temperature or higher, and a critical pressure It means a fluid that is in the above state. The supercritical fluid is not particularly limited and can be appropriately selected depending on the purpose, but a fluid with a low critical temperature is preferred.
The subcritical fluid is not particularly limited as long as it exists as a high-pressure liquid in the temperature and pressure regions near the critical point, and can be appropriately selected according to the purpose. Fluids listed as supercritical fluids can also be suitably used as subcritical fluids.

Examples of supercritical fluids include carbon monoxide, carbon dioxide, ammonia, nitrogen, water, alcohol solvents, hydrocarbon solvents, halogen solvents, and ether solvents.
Examples of alcohol solvents include methanol, ethanol, n-butanol and the like.
Examples of hydrocarbon solvents include ethane, propane, 2,3-dimethylbutane, benzene, and toluene. Halogen solvents include, for example, methylene chloride and chlorotrifluoromethane.
Ether solvents include, for example, dimethyl ether.
These may be used individually by 1 type, and may use 2 or more types together.
Among these, carbon dioxide is preferable because it has a critical pressure of 7.3 MPa and a critical temperature of 31° C., so that a supercritical state can be easily created, and it is nonflammable and easy to handle.

The critical temperature and critical pressure of the supercritical fluid are not particularly limited and can be appropriately selected according to the purpose. The critical temperature of the supercritical fluid is preferably −273° C. or higher and 300° C. or lower, more preferably 0° C. or higher and 200° C. or lower.

In addition to supercritical fluids and subcritical fluids, organic solvents and entrainers can also be used in combination. By adding an organic solvent and an entrainer, it is possible to more easily adjust the solubility in the supercritical fluid.
The organic solvent is not particularly limited and can be appropriately selected depending on the intended purpose. Examples thereof include ketone solvents, ester solvents, ether solvents, amide solvents, halogenated hydrocarbon solvents, and hydrocarbon solvents.
Ketone solvents include, for example, acetone, methyl ethyl ketone, methyl isobutyl ketone, and the like.
Ester solvents include, for example, ethyl formate, ethyl acetate, n-butyl acetate and the like.
Ether solvents include, for example, diisopropyl ether, dimethoxyethane, tetrahydrofuran, dioxolane, dioxane and the like.
Amide solvents include, for example, N,N-dimethylformamide, N,N-dimethylacetamide, N-methyl-2-pyrrolidone and the like.
Halogenated hydrocarbon solvents include, for example, dichloromethane, chloroform, bromoform, methyl iodide, dichloroethane, trichloroethane, trichloroethylene, chlorobenzene, o-dichlorobenzene, fluorobenzene, bromobenzene, iodobenzene, 1-chloronaphthalene and the like. .
Examples of hydrocarbon solvents include n-pentane, n-hexane, n-octane, 1,5-hexadiene, cyclohexane, methylcyclohexane, cyclohexadiene, benzene, toluene, o-xylene, m-xylene, p-xylene, Examples include ethylbenzene and cumene.
These may be used individually by 1 type, and may use 2 or more types together.

Moreover, after laminating the hole transporting material on the perovskite layer, the pressing process may be performed. The press treatment brings the hole-transporting material into closer contact with the perovskite layer, which may improve power generation efficiency.
The method of press treatment is not particularly limited and can be appropriately selected according to the purpose. IR (infrared spectroscopy) press molding method using a flat plate as typified by a tablet press, rollers, etc. A roll press method and the like can be mentioned.
The pressure during pressing is preferably 10 kgf/cm 2 or more, more preferably 30 kgf/cm 2 or more.
The time for the press treatment is not particularly limited and can be appropriately selected depending on the purpose, but is preferably 1 hour or less. Also, heat may be applied during the press treatment.

During the press treatment, a release agent may be interposed between the press and the electrode.
The release agent is not particularly limited and can be appropriately selected depending on the intended purpose. Fluororesins such as fluorinated resins, polyvinylidene fluoride, ethylene tetrafluoroethylene copolymers, ethylene chlorotrifluoroethylene copolymers, polyvinyl fluoride, and the like. These may be used individually by 1 type, and may use 2 or more types together.

<Film containing metal oxide>
A film containing a metal oxide may be provided between the hole transport layer and the second electrode after the press treatment step and before providing the second electrode.
The metal oxide is not particularly limited and can be appropriately selected depending on the intended purpose. Examples thereof include molybdenum oxide, tungsten oxide, vanadium oxide and nickel oxide. These may be used individually by 1 type, and may use 2 or more types together. Among these, molybdenum oxide is preferred.
The method of providing a film containing a metal oxide on the hole transport layer is not particularly limited and can be appropriately selected depending on the purpose. A wet film-forming method and the like can be mentioned.

As a wet film-forming method for forming a film containing a metal oxide, a method of preparing a paste in which metal oxide powder or sol is dispersed and applying the paste onto the hole transport layer is preferred.
The wet film-forming method is not particularly limited and can be appropriately selected depending on the intended purpose. etc. Moreover, as the wet printing method, for example, letterpress, offset, gravure, intaglio, rubber plate, screen printing, and the like may be used.

The average thickness of the film containing the metal oxide is not particularly limited and can be appropriately selected depending on the purpose, but is preferably 0.1 nm or more and 50 nm or less, more preferably 1 nm or more and 10 nm or less.

<Second electrode>
In the photoelectric conversion element, the second electrode is formed so as to separate the first electrode, the electron transport layer, and the perovskite layer, and is preferably formed on the hole transport layer or the metal oxide film. Electron diffusion can be prevented by forming the second electrode so as to separate the first electrode, the electron transport layer, and the perovskite layer in the photoelectric conversion element. Moreover, the same thing as a 1st electrode can be used for a 2nd electrode.

The shape, structure, and size of the second electrode are not particularly limited, and can be appropriately selected according to the purpose.
Examples of materials for the second electrode include metals, carbon compounds, conductive metal oxides, and conductive polymers.
Examples of metals include platinum, gold, silver, copper, and aluminum.
Carbon compounds include, for example, graphite, fullerene, carbon nanotubes, and graphene.
Examples of conductive metal oxides include ITO, FTO, and ATO.
Examples of conductive polymers include polythiophene and polyaniline.
These may be used individually by 1 type, and may use 2 or more types together.

The second electrode can be appropriately formed on the hole transport layer by using a method such as coating, lamination, vacuum deposition, CVD, or bonding, depending on the type of material used and the type of hole transport layer.

Moreover, in the photoelectric conversion element, at least one of the first electrode and the second electrode is preferably substantially transparent. For example, it is preferable to make the first electrode transparent so that the incident light is incident from the first electrode side. In this case, it is preferable to use a material that reflects light for the second electrode, such as metal, glass deposited with a conductive oxide, plastic, or a metal thin film. It is also effective to provide an antireflection layer on the electrode on the incident light side.

<Second substrate>
In the solar cell module of the present invention, the second substrate can also be arranged facing the first substrate so as to sandwich the photoelectric conversion element.
The shape, structure, and size of the substrate are not particularly limited, and can be appropriately selected according to the purpose.
The material of the second substrate is not particularly limited and can be appropriately selected depending on the intended purpose. Examples thereof include glass, plastic film, and ceramics.

An uneven portion may be formed in the joint portion between the second substrate and a sealing member to be described later, in order to improve adhesion.
The method for forming the concave-convex portion is not particularly limited and can be appropriately selected depending on the intended purpose. be done.
As a method of increasing the adhesion between the second substrate and the sealing member, for example, a method of removing organic substances on the surface of the second substrate or a method of improving the hydrophilicity of the second substrate may be used. The means for removing the organic substances on the surface of the second substrate is not particularly limited and can be appropriately selected according to the purpose. Examples thereof include UV ozone cleaning and oxygen plasma treatment.

<Sealing member>
The sealing member is arranged between the first substrate and the second substrate to seal the photoelectric conversion element.
The material of the sealing member is not particularly limited and can be appropriately selected according to the purpose. Examples thereof include cured acrylic resins and cured epoxy resins.
As the cured acrylic resin, any known material can be used as long as it is a cured monomer or oligomer having an acrylic group in the molecule.
As the cured epoxy resin, any known material can be used as long as it is a cured monomer or oligomer having an epoxy group in the molecule.

Examples of acrylic resins include water-dispersed, solventless, solid, heat-curable, curing agent-mixed, and ultraviolet-curable. Among these, the thermosetting type and the ultraviolet curable type are preferred, and the ultraviolet curable type is more preferred. It should be noted that even if it is an ultraviolet curing type, it is possible to heat, and it is preferable to heat even after ultraviolet curing.

Examples of epoxy resins include bisphenol A type, bisphenol F type, novolac type, cyclic aliphatic type, long chain aliphatic type, glycidylamine type, glycidyl ether type, glycidyl ester type, and the like. These may be used individually by 1 type, and may use 2 or more types together.

It is preferable to mix a curing agent and various additives with the epoxy resin as necessary.

The curing agent is not particularly limited and can be appropriately selected depending on the intended purpose.
Examples of amine curing agents include aliphatic polyamines such as diethylenetriamine and triethylenetetramine, and aromatic polyamines such as metaphenylenediamine, diaminodiphenylmethane and diaminodiphenylsulfone.
Acid anhydride-based curing agents include, for example, phthalic anhydride, tetra- and hexahydrophthalic anhydride, methyltetrahydrophthalic anhydride, methylnadic anhydride, pyromellitic anhydride, hetic anhydride, and dodecenylsuccinic anhydride. .
Other curing agents include, for example, imidazoles and polymercaptans. These may be used individually by 1 type, and may use 2 or more types together.

The additive is not particularly limited and can be appropriately selected depending on the intended purpose. , plasticizers, coloring agents, flame retardant aids, antioxidants, organic solvents, and the like. Among these, fillers, gap agents, curing accelerators, polymerization initiators, and desiccants (hygroscopic agents) are preferred, and fillers and polymerization initiators are more preferred.

By including a filler as an additive, it suppresses the infiltration of moisture and oxygen, further reduces volume shrinkage during curing, reduces outgassing during curing or heating, improves mechanical strength, improves thermal conductivity, Effects such as fluidity control can be obtained. Therefore, including a filler as an additive is very effective in maintaining stable output in various environments.

Further, regarding the output characteristics and durability of the photoelectric conversion element, not only the effects of intruding moisture and oxygen, but also the effects of outgassing generated during curing or heating of the sealing member cannot be ignored. In particular, the influence of outgassing generated during heating has a great influence on the output characteristics in high-temperature environment storage.
By including a filler, a gap agent, and a desiccant in the sealing member, these themselves can suppress the infiltration of moisture and oxygen, and the amount of the sealing member used can be reduced, thereby obtaining the effect of reducing outgassing. can be done. Including a filler, a gap agent, and a desiccant in the sealing member is effective not only during curing but also during storage of the photoelectric conversion element in a high-temperature environment.

The filler is not particularly limited and can be appropriately selected depending on the intended purpose. fillers and the like. These may be used individually by 1 type, and may use 2 or more types together.
The average primary particle size of the filler is preferably 0.1 μm or more and 10 μm, more preferably 1 μm or more and 5 μm or less. When the average primary particle diameter of the filler is within the above preferable range, the effect of suppressing penetration of moisture and oxygen can be sufficiently obtained, the viscosity becomes appropriate, and the adhesion to the substrate and defoaming properties are improved. It is also effective for controlling the width of the sealing portion and for workability.
The content of the filler is preferably 10 parts by mass or more and 90 parts by mass or less, more preferably 20 parts by mass or more and 70 parts by mass or less, relative to the entire sealing member (100 parts by mass). When the content of the filler is within the above preferable range, the effect of suppressing penetration of moisture and oxygen is sufficiently obtained, the viscosity becomes appropriate, and the adhesion and workability become good.

Gap agents are also called gap control agents or spacer agents. By including the gap material as an additive, it becomes possible to control the gap of the seal. For example, when a sealing member is provided on the first substrate or the first electrode, and the second substrate is placed thereon for sealing, the sealing member must be mixed with a gap agent. As a result, the gap of the sealing portion is aligned with the size of the gap agent, so that the gap of the sealing portion can be easily controlled.
The gap agent is not particularly limited as long as it is granular, has a uniform particle size, and has high solvent resistance and heat resistance, and can be appropriately selected according to the purpose. The gap agent preferably has a high affinity with the epoxy resin and has a spherical particle shape. Specifically, glass beads, silica fine particles, organic resin fine particles and the like are preferable. These may be used individually by 1 type, and may use 2 or more types together.
The particle diameter of the gap agent can be selected according to the gap of the sealing portion to be set, but is preferably 1 μm or more and 100 μm or less, more preferably 5 μm or more and 50 μm or less.

The polymerization initiator is not particularly limited as long as it initiates polymerization using heat or light, and can be appropriately selected depending on the purpose. Examples include thermal polymerization initiators and photopolymerization initiators. be done.

A thermal polymerization initiator is a compound that generates active species such as radicals and cations by heating. and peroxides such as A benzenesulfonic acid ester, an alkylsulfonium salt, or the like is used as the thermal cationic polymerization initiator.
On the other hand, as the photopolymerization initiator, a photocationic polymerization initiator is preferably used in the case of an epoxy resin. When a cationic photopolymerization initiator is mixed with an epoxy resin and irradiated with light, the cationic photopolymerization initiator decomposes to generate an acid, which causes polymerization of the epoxy resin and a curing reaction proceeds. A photocationic polymerization initiator has effects such as little volume shrinkage during curing, no oxygen inhibition, and high storage stability.

Examples of photocationic polymerization initiators include aromatic diazonium salts, aromatic iodonium salts, aromatic sulfonium salts, metacelone compounds, and silanol/aluminum complexes.
A photoacid generator having a function of generating an acid upon irradiation with light can also be used as the polymerization initiator. The photoacid generator acts as an acid that initiates cationic polymerization, and includes, for example, ionic sulfonium salt-based and iodonium salt-based onium salts composed of a cation portion and an anion portion. These may be used individually by 1 type, and may use 2 or more types together.

The amount of the polymerization initiator added may vary depending on the material used, but is preferably 0.5 parts by mass or more and 10 parts by mass or less, and 1 part by mass or more and 5 parts by mass with respect to the entire sealing member (100 parts by mass). Part or less is more preferable. By setting the amount to be added within the above preferred range, curing proceeds appropriately, the amount of uncured material remaining can be reduced, and excessive outgassing can be prevented.

A desiccant, also called a hygroscopic agent, is a material that has the function of physically or chemically adsorbing and absorbing moisture, and by including it in the sealing member, it is possible to further increase moisture resistance and reduce the effects of outgassing. .
The desiccant is not particularly limited and can be appropriately selected depending on the purpose, but is preferably particulate, such as calcium oxide, barium oxide, magnesium oxide, magnesium sulfate, sodium sulfate, calcium chloride, Examples include inorganic water-absorbing materials such as silica gel, molecular sieves, and zeolites. Among these, zeolites with high moisture absorption are preferred. These may be used individually by 1 type, and may use 2 or more types together.

A curing accelerator, also called a curing catalyst, is a material that increases the curing rate and is mainly used for thermosetting epoxy resins.
The curing accelerator is not particularly limited and can be appropriately selected depending on the intended purpose. tertiary amines or tertiary amine salts such as diazabicyclo(4,3,0)-nonene-5), imidazoles such as 1-cyanoethyl-2-ethyl-4-methylimidazole and 2-ethyl-4-methylimidazole, Phosphines such as triphenylphosphine and tetraphenylphosphonium/tetraphenylborate, and phosphonium salts are included. These may be used individually by 1 type, and may use 2 or more types together.

The coupling agent is not particularly limited as long as it is a material that has the effect of increasing molecular bonding strength, and can be appropriately selected according to the purpose. Examples thereof include silane coupling agents, and more specifically, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, N-phenyl-γ -aminopropyltrimethoxysilane, N-(2-aminoethyl)3-aminopropylmethyldimethoxysilane, N-(2-aminoethyl)3-aminopropylmethyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3- Silane coupling agents such as mercaptopropyltrimethoxysilane, vinyltrimethoxysilane, N-(2-(vinylbenzylamino)ethyl)3-aminopropyltrimethoxysilane hydrochloride, 3-methacryloxypropyltrimethoxysilane, and the like. be done. These may be used individually by 1 type, and may use 2 or more types together.

Epoxy resin compositions commercially available as sealing materials, sealing materials, adhesives, or the like are known as sealing members, and can be effectively used in the present invention. Among others, there are epoxy resin compositions developed and marketed for use in solar cells and organic EL devices, which can be used particularly effectively in the present invention. Commercially available epoxy resin compositions include, for example, TB3118, TB3114, TB3124, TB3125F (manufactured by ThreeBond Co., Ltd.), WorldRock5910, WorldRock5920, WorldRock8723 (manufactured by Kyoritsu Chemical Co., Ltd.), WB90US (P) (manufactured by Moresco Co., Ltd.), and the like. mentioned.

In the present invention, a sheet-like sealing material can be used as the sealing member.
The sheet-like sealing material is a sheet on which an epoxy resin layer is formed in advance, and the sheet is made of glass, a film having a high gas barrier property, or the like. The sealing member and the second substrate can be formed at once by attaching the sheet-like sealing material to the second substrate and then curing the same. It is also possible to have a structure with a hollow portion depending on the formation pattern of the epoxy resin layer formed on the sheet.

The method for forming the sealing member is not particularly limited and can be appropriately selected depending on the intended purpose. is mentioned. As a method for forming the sealing member, for example, letterpress, offset, gravure, intaglio, rubber plate, screen printing, or the like may be used.
Furthermore, a passivation layer may be provided between the sealing member and the second electrode. The passivation layer is not particularly limited as long as it is arranged so that the sealing member is not in contact with the second electrode, and can be appropriately selected depending on the purpose. Examples include aluminum oxide, silicon nitride, and silicon oxide. is mentioned.

<Other parts>
Other members are not particularly limited and can be appropriately selected according to the purpose.

An embodiment for carrying out the present invention will be described below with reference to the drawings. In each drawing, the same components are denoted by the same reference numerals, and redundant description may be omitted.

<Structure of solar cell module>
FIG. 10 is a cross-sectional view showing an example of the cross-sectional structure of the solar cell module of the present invention. As shown in FIG. 10, the solar cell module 100 has a photoelectric conversion element 11a and a photoelectric conversion element 11b. Each of the photoelectric conversion elements 11a and 11b includes a first electrode 2, a dense layer 3, a porous electron transport layer (porous layer) 4, a perovskite layer 5, a hole transport layer 6, a second on a first substrate 1, a photoelectric conversion element having an electrode 7 of The photoelectric conversion elements 11a and 11b are adjacent to each other, the first electrodes are electrically connected to each other, and the electron transport layer, the perovskite layer, and the hole transport layer are separated by a gap. In at least one of photoelectric conversion elements 11 a and 11 b , first electrode 2 , dense layer 3 , porous layer 4 and perovskite layer 5 are separated by hole transport layer 6 .
Since the first electrode 2, the dense layer 3, the porous layer 4, and the perovskite layer 5 are separated by the hole transport layer 6, the solar cell module 100 has less recombination of electrons due to diffusion. Therefore, it is possible to maintain power generation efficiency even after being exposed to high-intensity light for a long time. In addition, the first electrode 2 and the second electrode 7 have a conductive path to an electrode extraction terminal.
Further, in the solar cell module 100, the second substrate 10 is arranged to face the first substrate 1 so as to sandwich the photoelectric conversion element, and the sealing member 9 is provided between the first substrate 1 and the second substrate. It is arranged between the substrates 10 .
In the photoelectric conversion elements 11a and 11b, the first electrodes are electrically connected to each other, and the electron transport layer, the perovskite layer and the hole transport layer are separated by a gap. The void may be filled with gas or may be a vacuum.
The width of the gap is not particularly limited and can be appropriately selected according to the purpose, but is preferably 0.03 mm or more and 1 mm or less, more preferably 0.05 mm or more and 0.2 mm or less.

Photoelectric conversion elements of solar cell module 100 are sealed by first substrate 1 , sealing member 9 and second substrate 10 . Therefore, it is possible to control the water content and oxygen concentration in the hollow portion existing between the second electrode 7 and the second substrate 10 . By controlling the moisture content and oxygen concentration in the hollow portion of the solar cell module 100, power generation performance and durability can be improved. That is, the solar cell module is arranged between a second substrate facing the first substrate so as to sandwich the photoelectric conversion element, and between the first substrate and the second substrate. By further including a sealing member for sealing, the water content and oxygen concentration in the hollow portion can be controlled, so that power generation performance and durability can be improved.
The oxygen concentration in the hollow portion is not particularly limited and can be appropriately selected according to the purpose. More preferably 1% or more and 5% or less.

Moreover, in the solar cell module 100, since the second electrode 7 and the second substrate 10 are not in contact with each other, it is possible to prevent the second electrode 7 from being peeled off or broken.

In the solar cell module 100, the photoelectric conversion elements 11a and 11b are electrically connected. Specifically, the solar cell module 100 has a penetrating portion 8 that electrically connects the high electron conversion element 11a and the high electron conversion element 11b. A plurality of the through-holes 8 may be formed in a circular shape as shown in FIG. good.
By forming the second electrode after forming the penetrating portion 8, the material of the second electrode is formed on the side surface of the penetrating portion 8, making it possible to electrically connect adjacent photoelectric conversion elements. become. As the conductive material formed on the side surface of the penetrating portion 8, it is possible to use a material different from the material of the second electrode.
As described above, in the solar cell module 100, the second electrode 7 of the photoelectric conversion element 11a and the first electrode 2 of the photoelectric conversion element 11b are electrically connected by the penetrating portion 8 penetrating the hole transport layer 6. By being connected, the photoelectric conversion element 11a and the photoelectric conversion element 11b are connected in series. Although it is possible to connect a plurality of photoelectric conversion elements in parallel, the open-circuit voltage of the solar cell module can be increased by connecting the plurality of photoelectric conversion elements in series.

The penetrating portion 8 may penetrate the first electrode 2 and reach the first substrate 1 , or may stop processing inside the first electrode 2 and reach the first substrate 1 . It doesn't have to be. When the shape of the penetrating portion 8 is a fine hole that penetrates the first electrode 2 and reaches the first substrate 1, if the total opening area of the fine holes becomes too large with respect to the area of the penetrating portion 8, the A decrease in the film cross-sectional area of the electrode 2 of 1 increases the resistance value, which may cause a decrease in the photoelectric conversion efficiency. Therefore, the ratio of the total opening area of the fine holes to the area of the penetrating portion 8 is preferably 5/100 or more and 60/100 or less.

The method for forming the penetrating portion is not particularly limited, and can be appropriately selected according to the purpose. is mentioned. Among these, the laser processing method is preferable because the through portion 8 can be formed without using sand, etching, resist, or the like, and can be processed cleanly and with good reproducibility. The reason why the laser processing method is preferable is that the dense layer 3, the porous electron transport layer (porous layer) 4, the perovskite layer 5, the hole transport layer 6, and the second electrode 7 are formed when the through portion 8 is formed. At least one of them can be removed by impact peeling using a laser processing method. As a result, there is no need to provide a mask during lamination, and the removal of the material forming the photoelectric conversion element and the formation of the penetrating portion can be performed collectively and easily.

In at least one of photoelectric conversion element 11a and photoelectric conversion element 11b, first electrode 2, dense layer 3, porous layer 4, and perovskite layer 5 are separated by hole transport layer 6. FIG. The width of separation is preferably 50 μm or more.
The photoelectric conversion elements 11a and 11b are separated by the hole transport layer, and charge leaks from the photoelectric conversion elements 11a and 11b under the influence of hole diffusion in the hole transport layer. Therefore, it becomes difficult to maintain power generation efficiency even after being exposed to high-intensity light for a long time. That is, when the distance between the photoelectric conversion elements separated by the hole transport layer is 50 μm or more, it is possible to maintain power generation efficiency even after being exposed to high-intensity light for a long time.

The solar cell module of the present invention can be applied to a power supply device by combining it with a circuit board or the like that controls the generated current. Devices that use power supply devices include, for example, electronic desk calculators and wristwatches. Moreover, the power supply device having the photoelectric conversion element of the present invention can also be applied to mobile phones, electronic notebooks, electronic paper, and the like. A power source device having the photoelectric conversion element of the present invention can also be used as an auxiliary power source for extending the continuous use time of electric appliances of a rechargeable or dry battery type, or as a power source that can be used even at night by combining with a secondary battery or the like. can be used. Furthermore, it can also be used for IoT devices, artificial satellites, etc. as a self-sustaining power supply that does not require battery replacement or power supply wiring.

EXAMPLES The present invention will now be described with reference to examples and comparative examples. It should be noted that the present invention is not limited to the examples illustrated herein.

(Example 1)
<Fabrication of solar cell module>
An ITO (Indium Tin Oxide) glass substrate was used as the substrate and the first electrode.

A tin oxide colloidal solution (manufactured by Alpha Acer) was applied onto an ITO glass substrate and dried by heating at 100° C. for 1 hour. Then, a solution of (1-aminoethyl)phosphonic acid (manufactured by Aldrich) in ethanol 0.1 mM (where M means mol/dm ³ ) was applied onto the above film using a spin coating method. It was applied and dried at 70° C. for 10 minutes to obtain an electron transport layer.

Then, lead (II) iodide (0.5306 g), lead (II) bromide (0.0736 g), methylamine bromide (0.0224 g), formamidine iodide (0.1876 g), potassium iodide ( 0.0112 g) was added to N,N-dimethylformamide (0.8 ml) and dimethyl sulfoxide (0.2 ml), and the solution obtained by heating and stirring at 60° C. was spin-coated on the above electron transport layer. Chlorobenzene (0.3 ml) was added while coating with , to form a perovskite film, and dried at 150° C. for 30 minutes to form a perovskite layer. The average thickness of the perovskite layer was adjusted to 200 to 350 nm (Fig. 1).

Then, a groove was formed so that the distance between adjacent laminates was 10 μm by performing laser processing on the laminate obtained by the above process (FIG. 2). Then, 36.8 mg of the polymer represented by (A-5) (weight average molecular weight = 20,000, ionization potential 5.22 eV), and 7.4 mg of the additive represented by (B-14) as an additive. Weighed and dissolved in 3.0 ml of chlorobenzene. The resulting solution was applied onto the layered product obtained by the above process using a spin coating method to prepare a hole transport layer. The average thickness of the hole transport layer (the portion on the perovskite layer) was set to 50 to 120 nm (FIG. 3). Then, laser processing was performed to form holes penetrating all of the ITO (2) to the hole transport layer (6) (hereinafter sometimes referred to as through holes). A cross-sectional view is shown in FIG. 4, and a top view is shown in FIG.
Furthermore, 100 nm of gold was vacuum-deposited on the above laminate (FIG. 6).

After that, the edges of the first substrate and the second substrate on which the sealing members are provided, and the perovskite layer were etched by laser processing, and it was confirmed that the adjacent photoelectric conversion elements were connected in series ( Fig. 7 shows a cross-sectional view, and Fig. 8 shows a top view. Note that the number of photoelectric conversion elements connected in series is two.

Subsequently, the edge of the first substrate is coated with an ultraviolet curable resin (manufactured by Three Bond Holdings Co., Ltd., product name: TB3118) with a dispenser (manufactured by Sanei Tech Co., Ltd., product name: 2300N). After that, it is transferred to a glove box controlled to a low humidity (dew point -30 ° C.) and an oxygen concentration of 0.2%, a cover glass as a second substrate is placed on the ultraviolet curable resin, and the ultraviolet curable resin is irradiated with ultraviolet rays. was cured to seal the power generation region, and a solar cell module 1 in which two cells were directly connected as illustrated in FIG. 10 was produced.

<Evaluation of solar cell module>
The obtained solar cell module 1 was irradiated with light using a solar simulator (AM 1.5, 100 mW/cm ² ) and subjected to a solar cell evaluation system (manufactured by NF Circuit Design Block Co., Ltd., trade name: As-510-PV03). was used to evaluate solar cell characteristics (initial characteristics). Furthermore, using the above solar simulator, the solar cell characteristics (characteristics after 500 hours of continuous irradiation) were evaluated in the same manner as described above after continuously irradiating light for 500 hours under the same conditions as above.
The solar cell properties evaluated are open-circuit voltage, short-circuit current density, form factor, and conversion efficiency (power generation efficiency). Also, the ratio of the conversion efficiency in the characteristics after continuous irradiation for 500 hours to the conversion efficiency in the initial characteristics was determined as the conversion efficiency retention rate. Table 1 shows the results.

(Example 2)
In Example 1, 36.8 mg of the polymer represented by (A-5) and 7.4 mg of the additive (B-14) were combined with 36.8 mg of poly(3-n-hexylthiophene), lithium bis(trifluoro A solar cell module was produced in the same manner as in Example 1, except that 4.8 mg of methylsulfonylimide) and 6.8 mg of 4-t-butylpyridine were used. The properties of the obtained solar cell module were evaluated. Table 1 shows the results.

(Example 3)
In Example 1, lead (II) iodide (0.5306 g), lead (II) bromide (0.0736 g), methylamine bromide (0.0224 g), formamidine iodide (0.1876 g), iodine Potassium chloride (0.0112 g), N,N-dimethylformamide (0.8 ml), dimethyl sulfoxide (0.2 ml), lead (II) iodide (0.4841 g), antimony (III) iodide (0 .0502 g) lead (II) bromide (0.0736 g), methylamine bromide (0.0224 g), formamidine iodide (0.1876 g), potassium iodide (0.0112 g), N,N-dimethyl A solar cell module was produced in the same manner as in Example 1, except that formamide (0.8 ml) and dimethyl sulfoxide (0.2 ml) were used. The properties of the obtained solar cell module were evaluated. Table 1 shows the results.

(Example 4)
In Example 1, a tin oxide colloidal solution (manufactured by Alpha Acer) was coated on an ITO glass substrate, dried by heating at 100° C. for 1 hour, and then a solution obtained by diluting Peccell Technologies (PECC-B01) 10 times with ethanol. A solar cell module was fabricated in the same manner as in Example 1, except that a porous TiO ₂ layer was formed by coating with a spin coater. The properties of the obtained solar cell module were evaluated. Table 1 shows the results. A cross-sectional view of the device is also shown in FIG.

(Comparative example 1)
A solar cell module was fabricated in the same manner as in Example 1, except that the hole transport layer was formed so as not to separate the first electrode, the electron transport layer, and the perovskite layer. The properties of the obtained solar cell module were evaluated. Table 2 shows the results.

(Comparative example 2)
A solar cell was fabricated in the same manner as in Example 1, except that the second electrode was formed so as not to separate the first electrode, the electron transport layer, the perovskite layer, and the hole transport layer. Created a module. The properties of the obtained solar cell module were evaluated. Table 2 shows the results.

(Comparative Example 3)
A solar cell module was fabricated in the same manner as in Example 1, except that the perovskite layer did not contain a perovskite compound. The properties of the obtained solar cell module were evaluated. Table 2 shows the results.

From the results in Table 1, Examples 1 to 4 not only have very good initial characteristics, but also maintain a conversion efficiency retention rate of 80% or more after a 500-hour continuous irradiation test. It turns out that it has durability. On the other hand, in Comparative Example 1, it is clear that the maintenance rate of the conversion efficiency after the continuous irradiation test for 500 hours is low.

As described above, in the solar cell module of the present invention, in at least two mutually adjacent photoelectric conversion elements, the electron transport layer and the perovskite layer in at least two mutually adjacent photoelectric conversion elements are separated by the hole transport layer. ing. As a result, the solar cell module of the present invention can maintain power generation efficiency even after being exposed to high-intensity light for a long period of time.

一般式（２）において、Ａｒ１は置換もしくは無置換の芳香族炭化水素基を表し、Ａｒ２、Ａｒ３はそれぞれ独立に置換もしくは無置換の、単環式、非縮合多環式または縮合多環式芳香族炭化水素基の２価基を表す。Ａｒ４はベンゼン、チオフェン、ビフェニル、アントラセン、ナフタレンの２価基を表し、これらは置換基を有していてもよい。

一般式（３）において、Ｒ１～Ｒ５は水素原子、ハロゲン原子、アルキル基、アルコキシ基を表し、同一であっても異なっていても良い。Ｘはカチオンを表す。
＜４＞ 前記ペロブスカイト層が、Ｓｂ原子、Ｃｓ原子、Ｒｂ原子、及びＫ原子の少なくともいずれかを含有する、前記＜１＞から＜３＞のいずれかに記載の太陽電池モジュール。
＜５＞ 前記ペロブスカイト層と前記ホール輸送層との間にアミン化合物を含有する、前記＜１＞から＜４＞のいずれかに記載の太陽電池モジュール。
＜６＞ 前記電子輸送層が、少なくとも酸化スズを含有する、前記＜１＞から＜５＞のいずれかに記載の太陽電池モジュール。
＜７＞ 前記電子輸送層が、緻密層を有する、前記＜１＞から＜６＞のいずれかに記載の太陽電池モジュール。
＜８＞ 前記光電変換素子が直列又は並列に接続された、前記＜１＞から＜７＞のいずれかに記載の太陽電池モジュール。 Embodiments of the present invention are, for example, as follows.
<1> A solar cell module in which a plurality of photoelectric conversion elements each having a first electrode, an electron transport layer, a perovskite layer, a hole transport layer, and a second electrode are provided on a substrate,
In the two adjacent photoelectric conversion elements,
the first electrodes are electrically connected to each other;
the electron transport layer, the perovskite layer and the hole transport layer are separated by a gap;
the second electrode of one photoelectric conversion element and the first electrode of the other photoelectric conversion element are electrically connected,
A solar cell module in the one photoelectric conversion element, wherein the first electrode, the electron transport layer and the perovskite layer are separated by the hole transport layer.
<2> The solar cell module according to <1>, wherein the photoelectric layer contains a compound represented by the following general formula (1).
XαYβZγ General formula (1)
In general formula (1), the ratio of α:β:γ is 3:1:1, and β and γ represent integers greater than 1. X represents a halogen atom, Y represents an amino group-containing organic compound, and Z represents a metal ion.
<3> Any one of <1> to <2>, wherein the hole transport layer contains at least one of a compound represented by the following general formula (2) and a compound represented by the general formula (3) The solar cell module according to any one of the above.

In general formula (2), Ar1 represents a substituted or unsubstituted aromatic hydrocarbon group, Ar2 and Ar3 are each independently substituted or unsubstituted, monocyclic, non-fused polycyclic or condensed polycyclic aromatic represents a divalent group of group hydrocarbon groups. Ar4 represents a divalent group such as benzene, thiophene, biphenyl, anthracene or naphthalene, which may have a substituent.

In general formula (3), R1 to R5 each represent a hydrogen atom, a halogen atom, an alkyl group or an alkoxy group, and may be the same or different. X represents a cation.
<4> The solar cell module according to any one of <1> to <3>, wherein the perovskite layer contains at least one of Sb atoms, Cs atoms, Rb atoms, and K atoms.
<5> The solar cell module according to any one of <1> to <4>, containing an amine compound between the perovskite layer and the hole transport layer.
<6> The solar cell module according to any one of <1> to <5>, wherein the electron transport layer contains at least tin oxide.
<7> The solar cell module according to any one of <1> to <6>, wherein the electron transport layer has a dense layer.
<8> The solar cell module according to any one of <1> to <7>, wherein the photoelectric conversion elements are connected in series or in parallel.

According to the solar conversion module described in any one of <1> to <8>, various problems in the conventional art can be solved and the object of the present invention can be achieved.

JP 2016-195175 A

1 substrate (first substrate)
2 first electrode 3 dense layer 4 electron transport layer 5 perovskite layer 6 hole transport layer 7 second electrode 8 through hole 9 sealing member 10 second substrate 11a, 11b photoelectric conversion element

Claims (8)

A solar cell module in which a plurality of photoelectric conversion elements each having a first electrode, an electron transport layer, a perovskite layer, a hole transport layer, and a second electrode are provided on a substrate,
In the two adjacent photoelectric conversion elements,
the first electrodes are electrically connected to each other;
the electron transport layer, the perovskite layer and the hole transport layer are separated by a gap;
the second electrode of one photoelectric conversion element and the first electrode of the other photoelectric conversion element are electrically connected,
A solar cell module in the one photoelectric conversion element, wherein the first electrode, the electron transport layer and the perovskite layer are separated by the hole transport layer. The solar cell module according to claim 1, wherein the photoelectric conversion layer contains a compound represented by the following general formula (1).
XαYβZγ General formula (1)
In general formula (1), the ratio of α:β:γ is 3:1:1, and β and γ represent integers greater than 1. X represents a halogen atom, Y represents an amino group-containing organic compound, and Z represents a metal ion. 3. The solar cell according to claim 1, wherein the hole transport layer contains at least one of a compound represented by the following general formula (2) and a compound represented by the following general formula (3). module.

In general formula (2), Ar1 represents a substituted or unsubstituted aromatic hydrocarbon group, Ar2 and Ar3 are each independently substituted or unsubstituted, monocyclic, non-fused polycyclic or condensed polycyclic aromatic represents a divalent group of group hydrocarbon groups. Ar4 represents a divalent group such as benzene, thiophene, biphenyl, anthracene or naphthalene, which may have a substituent.

In general formula (3), R1 to R5 each represent a hydrogen atom, a halogen atom, an alkyl group or an alkoxy group, and may be the same or different. X represents a cation. 4. The solar cell module according to claim 1, wherein said perovskite layer contains at least one of Sb atoms, Cs atoms, Rb atoms and K atoms. 5. The solar cell module according to claim 1, containing an amine compound between said perovskite layer and said hole transport layer. The solar cell module according to any one of claims 1 to 5, wherein the electron transport layer contains at least tin oxide. 7. The solar cell module according to any one of claims 1 to 6, wherein said electron transport layer has a dense layer. The solar cell module according to any one of claims 1 to 7, wherein said photoelectric conversion elements are connected in series or in parallel.

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